Coated articles and methods of making the same

ABSTRACT

During an example coating method, a metallic substrate is provided. A foundation coat precursor is applied on the metallic substrate. The foundation coat precursor includes a matrix and a plurality of capsules present in the matrix. Each capsule includes a shell and a healing agent surrounded by the shell. A basecoat precursor is applied, and a clearcoat precursor is applied. The metallic substrate, the foundation coat precursor, the basecoat precursor, and the clearcoat precursor are heated i) after each respective application or ii) simultaneously, in order to cure the foundation coat, basecoat, and clearcoat precursors and respectively form a foundation coat, a basecoat, and a clearcoat. The foundation coat is ultraviolet (UV) stable and bonds the metallic substrate to the basecoat and the clearcoat.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/152,311 filed on May 11, 2016, which claims the benefit of U.S.Provisional Application No. 62/167,855, filed May 28, 2015. The entiredisclosures of each of the above applications are incorporated byreference herein in their entirety.

TECHNICAL FIELD

The present disclosure relates to coated articles, a coating method, anda method for enhancing corrosion resistance of a metallic substrate.

BACKGROUND

Metallic articles/objects (an example of which includes vehicle bodies)can be coated for several reasons. As an example, coating(s) may beapplied to provide the metallic article with an aesthetically pleasingappearance. As another example, coating(s) may be applied to provide themetallic article with a protective coating. The protective coating mayprotect the metallic article from the elements (e.g., rain, snow, ice,etc.), and/or from degradation due to moisture, salt exposure,oxidation, or the like.

SUMMARY

Some of the examples disclosed herein related to a coating method.During an example of the coating method, a metallic substrate isprovided. A foundation coat precursor is applied on the metallicsubstrate. The foundation coat precursor includes a matrix and aplurality of capsules present in the matrix. Each capsule includes ashell and a healing agent surrounded by the shell. A basecoat precursoris applied, and a clearcoat precursor is applied. The metallicsubstrate, the foundation coat precursor, the basecoat precursor, andthe clearcoat precursor are heated i) after each respective applicationor ii) simultaneously, in order to cure the foundation coat, basecoat,and clearcoat precursors and respectively form a foundation coat, abasecoat, and a clearcoat. The foundation coat is ultraviolet (UV)stable and bonds the metallic substrate to the basecoat and theclearcoat.

BRIEF DESCRIPTION OF THE DRAWINGS

Features of examples of the present disclosure will become apparent byreference to the following detailed description and drawings, in whichlike reference numerals correspond to similar, though perhaps notidentical, components. For the sake of brevity, reference numerals orfeatures having a previously described function may or may not bedescribed in connection with other drawings in which they appear.

FIG. 1 is a schematic side view of a vehicle including a vehicle body;

FIGS. 2A through 2C are schematic, cross-sectional views of a portion ofthe vehicle body shown FIG. 1, wherein the vehicle body includes ametallic substrate and coatings in accordance with an example of thepresent disclosure, and wherein FIG. 2A illustrates the portion prior toa disruption of the coatings on a metallic substrate, FIG. 2Billustrates disruption of the coatings and release of a healing agent inone of the coatings, and FIG. 2C illustrates a self-healed portion ofthe one of the coatings;

FIG. 3 is a schematic, cross-sectional view of a portion of the vehiclebody shown FIG. 1, wherein the vehicle body includes a metallicsubstrate and coatings in accordance with another example of the presentdisclosure; and

FIG. 4 is a flowchart of examples of the methods disclosed herein.

DETAILED DESCRIPTION

Metallic substrates may be used as a base for many objects, includingsheet panels, tools, equipment, automotive vehicle bodies, or the like.Metallic substrates may be formed of steel, aluminum, or magnesium. Itmay be desirable to coat metallic substrates, for aesthetics,protection, etc.

As noted, automotive vehicle bodies may include the metallic substrate.These metallic substrates may be coated with five layers or coats,namely: (a) a phosphate coat; (b) an electro-deposition coat (i.e.,e-coat); (c) a primer; (d) a basecoat; and (e) a clearcoat. Thephosphate coat promotes adhesion between the paint layers (e.g., e-coat,primer, basecoat, and clearcoat) and the metallic substrate (e.g., steelor aluminum). The e-coat provides corrosion protection. As used herein,the terms “electro-deposition coat” and “e-coat” refer to a coatingcreated using any suitable electro-deposition operation or process(i.e., an anti-corrosion electroplating bath). As used herein, the term“primer” means a coating capable of protecting the metallic substrateand the other coatings (e.g., phosphate coat, e-coat, basecoat, andclearcoat) against ultraviolet (UV) radiation from the sun or othersources. The primer therefore provides the vehicle body with UVradiation resistance. As used herein, the term “basecoat” means apolymeric coating including a color pigment, which imparts a color(e.g., red) to the vehicle body. Also as used herein, the term“clearcoat” refers to a polymeric coating that can provide gloss and/orprotection to the vehicle body. As such, the clearcoat may enhance theappearance of the vehicle body and may provide protection againstscratches, environmental elements, etc.

In examples of the method disclosed herein, a single coat (referred toherein as a foundation coat) replaces the phosphate coat, the e-coat,and in some instances, the primer. The foundation coat disclosed hereinincludes core-shell capsules, which have a healing agent as the core.When the foundation coat is damaged (e.g., by external forces, such asstone chipping, etc.), the shell of the capsule is disrupted. Disruptionof the shell releases the healing agent. The healing agent may beactivated when exposed to air or another healing agent. The activatedhealing agent(s) polymerizes, cures, or otherwise reseals the damagedfoundation coating. The self-healing property of the foundation coatingprovides enhanced corrosion resistance, in part because the resealedfoundation coating keeps the underlying metallic substrate from beingexposed to potentially corrosive elements. In addition to enhancedcorrosion resistance, the foundation coat disclosed herein providesadhesion promotion and UV radiation resistance.

The examples provided herein relate to a vehicle body as the coatedarticle. In these examples, the metallic substrate is coated withseveral coatings to form the vehicle body. In addition, it is to beunderstood that examples of the method(s) of the present disclosure maybe suitable for any components and/or subsystems (e.g., brake systems,suspension components, engine components, etc.) that may benefit fromcorrosion protection. Further, it is to be understood that the method(s)and article(s) disclosed herein are not limited to a vehicle body,components and/or subsystems, but rather the method(s) may be used tocoat, and the article(s) may be any metallic object for which it isdesirable to provide corrosion protection.

Referring now to FIG. 1, an example of a vehicle 10 is schematicallydepicted. The vehicle 10 includes a vehicle body 12 and wheels 13operatively coupled to the vehicle body 12. A tire 15 is operativelycoupled to each wheel 13. Although FIG. 1 illustrates a car, it is to beunderstood that the vehicle 10 may alternatively be a truck, motorcycle,or another kind of vehicle having a vehicle body 12.

An example of a portion of the vehicle body 12 is shown in cross-sectionin FIG. 2A. In this example, the vehicle body 12 includes the metallicsubstrate 14, the foundation coat 16 in direct contact with the metallicsubstrate 14, a basecoat 18 in direct contact with the foundation coat16, and a clear coat 20 in direct contact with the basecoat 18. Anotherexample of a portion of the vehicle body 12′ is shown in cross-sectionin FIG. 3. In this example, the vehicle body 12′ includes the metallicsubstrate 14, the foundation coat 16 in direct contact with the metallicsubstrate 14, a primer 22 in direct contact with the foundation coat 16,the basecoat 18 in direct contact with the primer 22, and the clear coat20 in direct contact with the basecoat 18. In FIGS. 2A and 3, each ofthe components 14, 16, 18, 20, 22 is undamaged. Each of the components14, 16, 18, 20, and 22 will be further described in reference to FIG. 4,which illustrates examples of the methods disclosed herein. It is to beunderstood that FIGS. 2A and 3 will also be referenced throughout thediscussion of FIG. 4.

Referring now to FIG. 4, an example of the method 100 for enhancingcorrosion resistance of the metallic substrate 14 is depicted, and anexample of the method 200 for coating the vehicle body 12, 12′ isdepicted. As depicted, the method 100 includes several of the same stepsas the method 200, and therefore, the methods 100, 200 will be discussedtogether.

Generally, the method 100 includes forming a foundation coat precursor(reference numeral 102), applying the foundation coat precursor on themetallic substrate 14 (reference numeral 104), applying the basecoatprecursor (reference numeral 106), applying the clearcoat precursor(reference numeral 108), and heating the metallic substrate 14, thefoundation coat precursor, the basecoat precursor, and the clearcoatprecursor i) after each respective application (reference numerals 105,107, 109) or ii) simultaneously (reference numeral 110), in order tocure the foundation coat precursor, the basecoat precursor, and theclearcoat precursor and to respectively form the foundation coat 16, thebasecoat 18, and the clearcoat 20.

Generally, the method 200 includes providing the metallic substrate 14(reference numeral 103), applying the foundation coat precursor on themetallic substrate 14 (reference numeral 104), applying the basecoatprecursor (reference numeral 106), applying the clearcoat precursor(reference numeral 108), and heating the metallic substrate 14, thefoundation coat precursor, the basecoat precursor, and the clearcoatprecursor i) after each respective application (reference numerals 105,107, 109) or ii) simultaneously (reference numeral 110), in order tocure the foundation coat precursor, the basecoat precursor, and theclearcoat precursor and to respectively form the foundation coat 16, thebasecoat 18, and the clearcoat 20. The method 200 may also begin withthe formation of the foundation coat precursor, as shown at referencenumeral 102.

It is to be understood that, in other examples of the methods 100, 200disclosed herein, the curing of the foundation coat precursor, thebasecoat precursor, and the clearcoat precursor to respectively form thefoundation coat 16, the basecoat 18, and the clearcoat 20 may beaccomplished by methods other than heating. In an example, thefoundation coat precursor, the basecoat precursor, and the clearcoatprecursor may be formulated to be cured by air drying at roomtemperature (from about 20° C. to about 25° C.) without heating (e.g.,if longer curing times are acceptable).

The formation of the foundation coat precursor will now be described.The foundation coat precursor is a precursor to the foundation coat 16.In the examples disclosed herein, the foundation coat 16 may be asol-gel coating, or a coating formed by a sol-gel process. During thesol-gel process, nanoparticles suspended in a liquid solution (i.e., asol) are invoked to interconnect/agglomerate and form a continuous,porous, nanostructured network of particles across the volume of theliquid medium (i.e., a gel). Drying the gel drives off the liquid andcauses the nanostructured network of particles to cross-link and cure,thereby forming the foundation coat 16.

In the examples disclosed herein, the foundation coat precursor includesa matrix and a plurality of capsules incorporated into the matrix. Thematrix of the foundation coat precursor may be in the form of the sol(i.e., nanoparticles suspended in a liquid solution).

The sol matrix of the foundation coat precursor includes nanoparticlessuspended in a liquid. An example of the sol matrix includes titaniananoparticles suspended in a liquid (e.g., water, ethanol, butylacetate, etc.). Another example of the sol matrix includes silicananoparticles suspended in a liquid (e.g., water, ethanol, butylacetate, etc.). In this example, the composition of the silicananoparticles can be expressed by the empirical formula SiO₂, or thepolymer formula (SiO₄)_(n) (where each silicon atom is attached by asingle bond to four oxygen atoms, which bridge to other silicon atoms).It is to be understood that not every silicon atom of every silicananoparticle may form four siloxane bridges (—Si—O—Si—) and insteadincludes one or more of its hydroxyl (—OH) or alkoxy (—OR) groups. Thesegroups are terminal groups that cover the surface of the silicananoparticles, and enable the silica nanoparticles to interconnect toform the gel.

The sol matrix may be formed from a nanoparticle source material, areactant, and a liquid that does not participate in the reaction betweenthe nanoparticle source material and the reactant. A catalyst may alsobe included that speeds up the chemical reaction(s) taking place in toform the sol.

The nanoparticle source material may be a silica nanoparticle sourcematerial, such as a silicon alkoxide (e.g., tetramethoxysilane ortetraethoxysilane) or a sodium silicate (e.g., Na₂SiO₃ or sodiummetasilicate, sodium polysilicate or (Na₂SiO₃)_(n), sodium orthosilicateor Na₄SiO₄, and the like). The nanoparticle source material may be atitania nanoparticle source material.

When the nanoparticle source material is a silicon alkoxide, the liquidmay be a solvent or solvent mixture (e.g., ethanol, acetone, butylacetate, or combinations thereof), and the reactant may be water or analcohol. Examples of a suitable catalyst include ammonium hydroxide orammonium fluoride. In this example, several reactions take place to formthe silica nanoparticles, and the sol. One of the reactions ishydrolysis, in which the silicon alkoxide reacts with the water to formsilanol (Si—OH) groups. These silanol groups can then react either witheach other or with another alkoxide group (Si—R) to form a siloxanebridge (Si—O—Si), which joins two molecules into one larger molecule. Asmentioned above, each silicon atom can form up to four siloxane bridges.This enables the initially small molecules to connect together to formlarger molecules (i.e., the silica nanoparticles) which contain, forexample, thousands of silicon-oxygen bridges.

When the nanoparticle precursor is a sodium silicate, the liquid may bewater, and the reactant may be an acid (e.g., hydrochloric acid orsulfuric acid). In this example, when the acid is added, hydrolysis willoccur and the silanol groups will form. The silicate molecules formsiloxane bonds with other silicate molecules and bridge together to formthe silica nanoparticles in the liquid, resulting in another example ofthe sol matrix.

At some point, the nanoparticles in the sol matrix reach a criticalpoint where they stop growing in size and instead agglomerate with othernanoparticles. This may be dependent on several factors, including thepH and concentration of other species in the sol matrix. The terminalhydroxyl and alkoxy groups on the surface of the nanoparticles allow thenanoparticles to interconnect with each other. When the nanoparticlesjoin together to form a continuous network spans the liquid solution,the gel has formed.

In the examples disclosed herein, the matrix of the foundation coatprecursor is the sol. Depending on the chemistry of the sol reactionsolution, gelation may naturally occur following sol formation. As anexample, the substrate may be dipped in to the sol matrix havingnanoparticles therein (i.e., the foundation coat precursor), and the gelforms as the substrate is removed from the sol matrix or after it isremoved from the matrix. The gel may then be air or bake cured to formthe foundation coat. In other instances, the onset of gelation mayrequire an additional catalyst, water, oxygen, a temperature changes, ormore time.

An example of forming a sol-gel coating follows.

A typical precursor uses metal alkoxides such as, e.g., siliconetetraethoxide [Si(OC₂H₅)₄, TEOS] in an ethanol solvent. Then the sol-gelcoating forms in four stages:

-   -   1) The precursor reacts with water such as humidity in the air        in a hydrolysis reaction:        -   a. Si(OC₂H₅)₄+H₂O→HO—Si(OC₂H₅)₃+C₂H₅OH; or        -   b. Si(OC₂H₅)₄+4H₂O→Si(OH)₄+4C₂H₅OH    -   2) Condensation and polymerization of monomers forms chains and        particles:        -   a. (OC₂H₅)₃Si—OH+HO—Si(OC₂H₅)₃→(OC₂H₅)₃Si—O—Si(OC₂H₅)₃+H₂O;            or        -   b.            (OC₂H₅)₃Si—OC₂H₅+HO—Si(OC₂H₅)₃→(OC₂H₅)₃Si—O—Si(OC₂H₅)₃+C₂H₅OH    -   Sol: nano-sized silica particles are synthesized from repeated        hydrolysis and condensation of silicon alkoxides.    -   3) The polymers continue to crosslink and grow into networks        throughout the liquid medium and form a gel. Gelation: silica        particles continue to grow and crosslink to form chains and a        networked structure, forming a gel.    -   4) The solvent evaporates either by heat or at room temperature        and forms a dense ceramic film on the substrate.

The sol matrix of the foundation coat precursor may also be purchased.As an example, the matrix of the foundation coat precursor may be one ofthe coatings sold by COVAL MOLECULAR COATINGS such as the coating soldunder the trade name COVAL METAL COAT™.

The foundation coat precursor also includes the previously mentionedcapsules in the sol matrix. The capsules may be mixed into the solmatrix as an additive. The capsules may be added, by weight percent withrespect to the weight of the sol matrix, in an amount ranging from about1 wt. % to about 40 wt. %. It is to be understood that this percentagemay be varied depending upon a desired level of self-healing. As anotherexample, the capsules may be added in an amount ranging from about 5 wt.% to about 10 wt. % of the total sol matrix wt. %. The capsules 24 areshown in FIGS. 2A and 3 in the foundation coat 16.

The capsules 24 include a shell 28 that surrounds a core 26. It is to beunderstood that the shell 28 may have any suitable thickness. In anexample, the thickness of the shell 28 ranges from about 1/20^(th) toabout ⅕^(th) of the diameter of the capsule 24. The shell 28 may beformed of any material that is chemically compatible with thenanoparticles in the sol, the gel, and ultimately the foundation coat16. By “chemically compatible,” it is meant that the shell 28 is capableof covalently bonding (e.g., cross-linking) to the foundation coat 16.For example, on shell material X, covalent bonds Si—O—X can be formedbetween shell material X and a silicone-based sol-gel coating.

In an example, each of the nanoparticles and the shell 28 are formed ofsilica (silicon dioxide) or titania. When the nanoparticles arebonded/cross-linked together during curing, the capsules 24 can alsoparticipate in cross-linking through the shell 28. Other examples of theshell 28 may include quartz crystal or silica glass.

The shell 28 is capable of being disrupted (i.e., broken, cracked,etc.), for example, when the vehicle body 12 is scratched, and thedisruption in the shell 28 releases the material making up the core 26.The disruption of the shell 28 and the release of the core 26 materialis shown in FIG. 2B, and the scratch is labeled 27.

The core 26 of the capsules 24 includes the healing agent. The healingagent is compatible with the dried and cured foundation coat 16. By“compatible,” it is meant that the healing agent is capable of adheringto the foundation coat 16. As an example, a suitable healing agent mayhave similar sol-gel coating chemistry as the matrix used to form thefoundation coat 16, and may also have air or oxygen activated curing.This type of healing agent, when released from the shell 28 may beexposed to air, activated, and polymerized or cross-linked to reseal thedamaged area of the foundation coat 16. The resealed portion 29 of thefoundation coat 16 is shown in FIG. 2C.

Examples of the self-healing agent include silicon based polymers,polyurethane polymers, or higher concentration alcohol-based sol-gelmaterials with nanoparticles therein (“higher” being, e.g., 40 wt. %SiO2 concentration as opposed to a, e.g., 25 wt. % normal SiO₂ solidcontent) (where the nanoparticle concentration is higher than thenanoparticle concentration in the sol matrix of the foundation coatprecursor).

In an example of the one-part system, the healing agent within the cores26 of the capsules 24 may include an unsaturated multi-functional resincapable of oxygen initiated cross-linking. The unsaturatedmultifunctional resin may be an alkyd resin. In an example, the alkydresin is formed from a fatty acid, a tri-functional alcohol, and an acidor acid anhydride. In another example, the alkyd resin includes atelechelic end group selected from the group consisting of an epoxy, anisocyanate, a polyol, a silanol, a vinyl terminated silane, a vinylgroup, an unsaturated fatty acid, and an unsaturated functional group.Examples of a one-part system are commercially available from AutonomicMaterials Inc., Champaign, Ill.

Other examples of the self-healing agent are two-part systems. Anexample of the two-part system is shown in FIG. 3. In these systems, thefoundation coat precursor and the formed foundation coat 16 includetherein a blend of first and second capsules 24, 24′. These capsules 24,24′ may have the same type of shell 28, but the cores 26, 26′ may beformed of two different healing agents. For example, the first capsules24 in a two-part system may include a curable resin as the core 26, andthe second capsules 24′ in a two-part system may include a curing agentof the curable resin as the core 26′. When the shells 28 of thesecapsules 24, 24′ are disrupted and the cores 26, 26′ come in contactwith one another, the curing agent core 26′ initiates the curing of thecurable resin core 26.

In an example of the two-part system, the healing agent within the cores26 of the capsules 24 may include an unsaturated multi-functional resincapable of oxygen initiated cross-linking. The unsaturatedmultifunctional resin may be an alkyd resin. In an example, the alkydresin is formed from a fatty acid, a tri-functional alcohol, and an acidor acid anhydride. In another example, the alkyd resin includes atelechelic end group selected from the group consisting of an epoxy, anisocyanate, a polyol, a silanol, a vinyl terminated silane, a vinylgroup, an unsaturated fatty acid, and an unsaturated functional group.The cores 26′ of capsules 24′ may include a catalyst or a curing agent.In an example, the catalyst is a metallic complex, the metal of themetallic complex being selected from the group consisting of cobalt,manganese, iron, cerium, vanadium, zirconium, bismuth, barium, aluminum,calcium, zinc, lithium, and potassium. An example of a curing agent isan epoxy curing agent.

In another example, the curable resin core 26 may be a vinyl-terminatedpolydimethylsiloxane resin and the curing agent core 26′ may be anysuitable curing agent for the vinyl-terminated polydimethylsiloxane(PDMS) resin. This particular two-part system is commercially availablein the AMI Series 1 from Autonomic Materials Inc., Champaign, Ill.

In yet another example of a two-part system, capsules 24 may include asthe core 26 a resin with reactive chemical groups (e.g., hydroxyls oramines); and capsules 24′ may include as the core 26′ a polyisocyanateresin capable of reacting with the core 26 resin. When the two capsules24, 24′ rupture and the two cores 26, 26′ mix together, a cross-linkingreaction occurs, and a new polyurethane protective coating forms.

The capsules 24, 24′ may be embedded and dispersed in the matrix usingany suitable dispersion technique. In an example, embedding anddispersing occur simultaneously. In an example, embedding and dispersingare accomplished using mechanical agitation after directly mixing thecapsules 24, 24′ into the sol matrix of the foundation coat precursor.It is to be understood that the agitation speed, material viscosity, andagitation time may affect whether the shell 28 is ruptured duringembedding and dispersing. Lower agitation speed, lower viscosity, andshorter agitation time results in a lower number of shells beingruptured during embedding and dispersing, however, these same parameterscan also lead to the capsules 24, 24′ being less uniformly dispersedthroughout the matrix.

The capsules 24, 24′ may be micro-sized or nano-sized. In one example,the capsules 24, 24′ are similarly sized to the nanoparticles in the solmatrix. In another example, the capsules 24, 24′ may contain silicananoparticles as the healing agent, and these capsules 24, 24′ may bemicro-sized.

As shown at reference numeral 103 in FIG. 4, the methods 100, 200 mayinclude providing the metallic substrate 14. Examples of the metallicsubstrate 14 include steel, magnesium, or aluminum. In an example, themetallic substrate 14 may be a vehicle body-in-white (BIW). As usedherein, the term “vehicle BIW” refers to the sheet metal components ofthe vehicle body that are welded together, including swing metals (e.g.,doors, hood, and decklid), but without moving parts (e.g., wheels andtires), the motor, chassis sub-assemblies, or trim (e.g., glass, seats,upholstery, electronics, etc.), and before painting. The metallicsubstrate 14 (e.g., vehicle BIW) may be supplied using a conveyer. Atthis point, all the sealers and adhesives in the vehicle BIW are fullycured or gelled.

Providing the metallic substrate 14 may also involve cleaning themetallic substrate 14 (e.g., vehicle BIW). For example, the vehicle BIWmay undergo a multi-stage cleaning process in order to removecontamination from the entire vehicle BIW. Water and cleaner may besprayed on the vehicle BIW to clean it. After the metallic substrate 14has been cleaned, the method 100, 200 continues to reference numeral104.

At reference numeral 104 in FIG. 4, the foundation coat precursor isapplied directly on the metallic substrate 14. In an example, thefoundation coat precursor is supplied in a tank or other suitablecontainer, and the metallic substrate 14 is dipped into the tank. Dipcoating applies the foundation coat precursor over the exposed surfacesof the metallic substrate 14, including all of the interior and exteriorsurfaces of the metallic substrate 14 (e.g., vehicle BIW). At thisstage, the foundation coat precursor is not cured.

Some examples of the methods 100, 200 involve the application of threeprecursors (including the foundation coat precursor) and one bake. Asused herein, the term “bake” means a process in which at least onepolymer coat is heated in an oven to cure that polymeric coat. Themethods 100, 200 involving the application of three precursors and onebake will now be described in reference to FIGS. 104, 106, 108, and 110.In these examples, the methods 100, 200 proceed from the application ofthe foundation coat precursor (reference numeral 104) to the applicationof the application of a basecoat precursor (reference numeral 106).

In one example, the basecoat precursor may include a monomer or polymerprecursor that polymerizes and crosslinks to form the basecoat 18 of thevehicle body 12, 12′ when exposed to the heating. In another example,the basecoat precursor may include a polymer that crosslinks to form thebasecoat 18 of the vehicle body 12, 12′ when exposed to the heating. Asexamples, the basecoat 18 may include acrylics, vinyls, polyurethanes,polycarbonates, polyesters, alkyds, polyepoxy, polysiloxanes, resins,and combinations thereof. As such, the basecoat precursor may includeany monomer, polymer precursor, or polymer that, after curing, will formthe basecoat 18. The basecoat precursor also includes a pigment thatimparts color (e.g., red, black, etc.) to the basecoat 18 and to thevehicle body 12, 12′.

In this example of the methods 100, 200, the basecoat precursor isdirectly applied over the foundation coat precursor before thefoundation coat precursor is cured. The metallic substrate 14 (e.g.,vehicle BIW) with the foundation coat precursor thereon is moved into abasecoat spraying booth. While in the basecoat spraying booth, thebasecoat precursor is sprayed over the foundation coat precursor that isalready on the metallic substrate 14. At this stage, the basecoatprecursor is not cured.

In this example of the methods 100, 200, the metallic substrate 14coated with the foundation coat precursor and the basecoat precursor maybe exposed to a heated flash oven before the clearcoat precursor isapplied in order to drive off solvent contained in the basecoat. Thismay prepare the basecoat for clearcoat precursor application.

In the methods 100, 200 involving the application of the threeprecursors and one bake , the methods 100, 200 then proceed from theapplication of the basecoat precursor (reference numeral 106) to theapplication of a clearcoat precursor (reference numeral 108).

The clearcoat precursor forms the clearcoat 20, which is a polymericcoating that can provide gloss and protection to the vehicle body 12,12′. An example of the clearcoat 20 is an acrylic based polymer.Examples of the clearcoat precursor may include a hydroxyl acrylic, apolyester carbamate acrylic, polyester, an epoxy, a blocked isocyanatesystem, or combinations thereof.

In this example of the methods 100, 200, the clearcoat precursor isdirectly applied over the basecoat precursor before the foundation coatprecursor and the basecoat precursor are cured. At reference numeral108, the metallic substrate 14 (e.g., vehicle BIW) with the foundationcoat precursor and the basecoat precursor applied thereon can beadvanced to a clearcoat spraying booth. While in the clearcoat sprayingbooth, the clearcoat 20 is sprayed on the basecoat precursor that isalready disposed over the foundation coat precursor and metallicsubstrate 14. At this stage, the clearcoat precursor is not cured.

In this example of the methods 100, 200, after applying the clearcoatprecursor over the basecoat precursor, the methods 100, 200 proceed tothe one bake (reference numeral 110). The one bake entails heating themetallic substrate 14 (e.g., vehicle BIW), foundation coat precursor,basecoat precursor, and clearcoat precursor simultaneously in order tocure all the precursors to form coats (i.e., foundation coat 16,basecoat 18, and clearcoat 20). Heating may be accomplished so that themetallic substrate 14 is heated in an oven at a temperature ranging fromabout 220 degrees Fahrenheit to about 320 degrees Fahrenheit for a timeranging from about 15 minutes to about 50 minutes. In an example, themetallic substrate 14 is heated in an oven at a temperature of about 280degrees Fahrenheit for 30 minutes. In this example, the metallicsubstrate 14, foundation coat precursor, basecoat precursor, andclearcoat precursor may be baked in an oven in order to cure theprecursors and form the respective coats in one bake. As discussedabove, the term “bake” means a process in which a precursor is heated inan oven to cure and form a polymeric coat. After heating, the vehiclebody 12, 12′ is formed and then removed from the oven.

Other examples of the methods 100, 200 involve a bake after theapplication of each of the three precursors. These examples methods 100,200 involve respective bakes at each of reference numerals 105, 107 and109. The methods 100, 200 involving individual bake steps will now bedescribed.

In these examples, the methods 100, 200 proceed from the application ofthe foundation coat precursor (reference numeral 104) to the first bake(reference numeral 105). At reference numeral 105 in FIG. 4, after thefoundation coat precursor is applied to the metallic substrate 14, thecoated substrate is exposed to heating (e.g., in an oven at atemperature of about 250 degrees Fahrenheit for about 20 minutes). Thebake at reference numeral 105 cures the foundation coat precursor toform the foundation coat 16.

This example of the method proceeds to reference numeral 106, where thebasecoat precursor is applied to the cured foundation coat 16. Thebasecoat precursor may be applied in a similar manner as previouslydescribed, except that the underlying foundation coat 16 is cured.

In these examples, the methods 100, 200 proceed from the application ofthe basecoat precursor (reference numeral 106) to a heated flash bake(e.g., the second bake shown at reference numeral 107). At referencenumeral 107 in FIG. 4, after the basecoat precursor is applied to thecured foundation coat 16, the coated substrate is exposed to heating. Inthis bake, the goal is not to cure the basecoat precursor to form thebasecoat 18, but rather is to dry the basecoat precursor to prepare thebasecoat precursor for the application of the clearcoat precursor. Theheated flash bake may be accomplished in an oven at 180 degreesFahrenheit for about 10 minutes.

This example of the method proceeds to reference numeral 108, where theclearcoat precursor is applied to the dried basecoat precursor. Theclearcoat precursor may be applied in a similar manner as previouslydescribed, except that the underlying foundation coat 16 is cured andthe underlying basecoat precursor is dried.

In these examples, the methods 100, 200 proceed from the application ofthe clearcoat precursor (reference numeral 108) to the third bake(reference numeral 109). At reference numeral 109 in FIG. 4, after theclearcoat precursor is applied to the dried basecoat precursor, thecoated substrate is exposed to heating. The third bake may beaccomplished in an oven at 280 degrees Fahrenheit for about 30 minutes.The bake at reference numeral 109 cures the dried basecoat precursor toform the basecoat 18 and the clearcoat precursor to form the clearcoat20.

Again referring back to reference numeral 104 where the foundationprecursor is applied to the metallic substrate 14, still other examplesof the methods 100, 200 may proceed to reference numeral 112, where aprimer precursor is applied to the uncured foundation coat precursor. Atreference numeral 112, the metallic substrate 14 (e.g., vehicle BIW)having the foundation coat precursor thereon is positioned in a primerspraying booth. While in the primer spraying booth, the primer precursoris sprayed directly over the foundation coat precursor that is alreadydisposed on the metallic substrate 14.

After the primer precursor application, the methods 100, 200 thenproceed to the bake at reference numeral 105. In this example, the bakeat reference numeral 105 entails heating the metallic substrate 14, thefoundation coat precursor, and the primer precursor in order to cure thefoundation coat precursor and the primer precursor to form,respectively, the foundation coat 16 and the primer 22. To perform thebake, the metallic substrate 14 coated with the foundation coatprecursor and the primer precursor may be placed in an oven and heatedto a suitable curing temperature. After being cured, the primerprecursor forms the primer 22 (FIG. 3). The primer 22 is a coating thatis capable of protecting the metallic substrate 14 and the other coats(i.e., foundation coat 16, basecoat 18, and clearcoat 20) against UVradiation exposure.

After curing at reference numeral 105, the foundation coat 16 and theprimer 22 are formed, and the methods 100, 200 may proceed to referencenumeral 106, where the basecoat precursor is applied in a similar manneras previously described. As one example, the methods 100, 200 maycontinue then with reference numerals 108 (clearcoat precursorapplication) and 110 (heating to form basecoat 18 and clearcoat 20). Asanother example, the methods 100, 200 may continue with referencenumerals 107 (heating to form basecoat 18), 108 (clearcoat precursorapplication), and 109 (heating to form clearcoat 20).

After the precursors are cured and the coats 16, 18, 20 (and in someinstances 22) are formed, the methods 100, 200 may further includeadditional processes. At reference numeral 114, the vehicle body 12, 12′may be inspected to identify defects. For example, the vehicle body 12,12′ may be subjected to a quality inspection. If the vehicle body 12,12′ passes the quality inspection, the vehicle body 12, 12′ is sent to ageneral assembly area at reference numeral 120. At the general assemblyarea, the vehicle body 12, 12′ is coupled to the other components of thevehicle 10. Conversely, if the vehicle body 12, 12′ fails the qualityinspection because, for example, some defects are identified, themethods 100, 200 may proceed to reference numeral 116 or 118.

At reference numeral 116, the identified defects are repaired. Theserepairs may be conducted in-line by re-routing the vehicle body 12, 12′back to the basecoat spraying booth at reference numeral 106.Alternatively, at reference numeral 118, the repairs may be conductedoffline after the quality inspection at 114, and the vehicle body 12,12′ is sent to the general assembly area after the defects have beenrepaired.

It is to be understood that throughout the methods 100, 200 the metallicsubstrate 14 does not undergo an electro-deposition (ELPO) operation orprocess (i.e., an anti-corrosion electroplating bath) in order to createan ELPO coat or layer, which may be made of an epoxy based material. Inother words, the metallic substrate 14 (or any other part of the vehiclebody 12, 12′) is not subjected to an ELPO operation. The ELPO coat maybe referred to as an electro-deposition coat, an electrophoreticdeposition (EPD) coat, or an e-coat. Accordingly, the vehicle body 12,12′ does not include an electro-deposition coat.

The examples of the vehicle body 12 (FIG. 2A) and 12′ (FIG. 3) includeseveral coats, including the foundation coat 16, the basecoat 18, theclearcoat 20, and in some instances the primer 22.

An example of foundation coat 16 covalently bonding to metallicsubstrate 14 is shown below.

Hydrolysis reaction—silicone alkoxide precursor reacts with water;

Cross-linking and gel forming in the precursor;

Monomers attracted to the metal surface by hydrogen bonds; and

Condensation and continued cross-linking form a covalently bondedcoating film on the surface.

This foundation coat 16 is a polymeric coating that is inherently UVstable and is capable of protecting the vehicle body 12, 12′ againstcorrosion through self-healing, and helps bond the metallic substrate 14to other coatings. The term “inherently UV stable” means that thematerial forming the foundation coat 16, by itself and without any UVstable additives, does not crack or disintegrate when attacked byultraviolet radiation. As an example, the foundation coat 16 can berated UV-8. A material or coat rated UV-8 can withstand 8000 hours ofexposure to UV light before the elongation at break is reduced to 50% ofthe original value during testing in a Weather-OMeter. UV ratings (e.g.,UV-X) are expressed as a multiple of 1000 hours of exposure until achosen mechanical property (e.g., elongation at break or tensilestrength) reaches 50% of the original value (i.e., the value of themechanical property before the material was subjected to UV light). Asexamples, the UV rate of the foundation coat 16 may range between UV-5and UV-10.

With its self-healing property, the foundation coat 16 is able to repaircracks, scratches, or other disruptions in the foundation coat 16. Therepaired portions keep the underlying metallic substrate 14 from beingexposed to external elements, and thus enhance the corrosion resistanceof the vehicle body 12, 12′. In addition to the self-healing enhancingcorrosion resistance, the coat 16 itself protects the vehicle body 12,12′ against corrosion such that the corrosion rate (as expressed in milspenetration per year (mpy)) ranges between the 0.9 and 10 mpy. Forexample, the corrosion rate (as expressed in mpy) may be 3 mpy.

The capsules 24, 24′ in the foundation coat 16 may lead to the coat 16having increased surface roughness. To reduce the surface roughness, thecapsules 24, 24′ may be nano-sized. In an example, it may be desirablethat the nanoparticles in the matrix and the capsules 24, 24′ beapproximately the same size (e.g., having an average diameter from about700 nm to about 900 nm). Similarly sized particles lead to thefoundation coat 16 exhibiting surface smoothness.

In other examples, the capsules 24, 24′ may have a size/average diameterranging from about 1 micron to about 25 microns.

The foundation coat 16 is chemically bonded to the metallic substrate14. The term “chemically bonded” means that a chemical covalent or ionicbond couples the foundation coat 16 with the metallic substrate 14. Thefoundation coat 16 is therefore configured to establish a strongadhesion bond with the metallic substrate 14. As an example, the bondenergy of the chemical bond between the foundation coat 16 and themetallic substrate 14 may range between 600 kilojoule per mol (kJ/mol)and 800 kJ/mol. As an example, the bond energy of the chemical bondbetween the foundation coat 16 and the metallic substrate 14 may be 700kJ/mol.

When included, the primer 22 provides additional UV radiationresistance.

The basecoat 18 is a polymeric coating that is applied over thefoundation coat 16 or the primer 22. The basecoat 18 imparts color tothe vehicle body 12, 12′.

The clearcoat 20 is applied over the basecoat 18. The clearcoat 20 is apolymeric coating that can provide gloss and protection to the vehiclebody 12, 12′.

Reference throughout the specification to “one example”, “anotherexample”, “an example”, and so forth, means that a particular element(e.g., feature, structure, and/or characteristic) described inconnection with the example is included in at least one exampledescribed herein, and may or may not be present in other examples. Inaddition, it is to be understood that the described elements for anyexample may be combined in any suitable manner in the various examplesunless the context clearly dictates otherwise.

It is to be understood that the ranges provided herein include thestated range and any value or sub-range within the stated range. Forexample, a range from about 600 kilojoule per mol (kJ/mol) and 800kJ/mol should be interpreted to include not only the explicitly recitedlimits of from about 600 kJ/mol to about 800 kJ/mol, but also to includeindividual values, such as 650.5 kJ/mol, 700 kJ/mol, 795 kJ/mol, etc.,and sub-ranges, such as from about 650 kJ/mol to about 750 kJ/mol; fromabout 625 kJ/mol to about 775 kJ/mol, etc. Furthermore, when “about” isutilized to describe a value, this is meant to encompass minorvariations (up to +/−10%) from the stated value.

In describing and claiming the examples disclosed herein, the singularforms “a”, “an”, and “the” include plural referents unless the contextclearly dictates otherwise.

While several examples have been described in detail, it is to beunderstood that the disclosed examples may be modified. Therefore, theforegoing description is to be considered non-limiting.

What is claimed is:
 1. A coated article, comprising: a metallicsubstrate; a foundation coat bonded to the metallic substrate, whereinthe foundation coat comprises: cross-linked titania or silicananoparticles; and a plurality of capsules distributed among the crosslinked titania or silica nanoparticles, each capsule including a shellcapable of covalently bonding to the cross-linked titania or silicananoparticles and a healing agent surrounded by the shell, wherein thehealing agent is an alcohol based sol gel material comprising titania orsilica nanoparticles, and wherein the shell and the healing agent arechemically compatible with the cross linked titania or silicananoparticles.
 2. The coated article of claim 1, wherein the coatedarticle is free of any electro-deposition coatings.
 3. The coatedarticle of claim 1, wherein the foundation coat is ultraviolet radiation(UV) stable.
 4. The coated article of claim 1, wherein the plurality ofcapsules is a plurality of first capsules and the coated article furthercomprises a plurality of second capsules, wherein the first capsulesinclude a resin as a first healing agent, and where the second capsulesinclude a curing agent of the resin as a second healing agent.
 5. Thecoated article of claim 1, wherein the shell is selected from the groupconsisting of titania, silicon dioxide, quartz crystal, and silicaglass.
 6. The coated article of claim 1 wherein the shell has athickness of greater than or equal to about 1/20th to less than or equalto about ⅕th of a diameter of the capsule.
 7. The coated article ofclaim 1 wherein the metallic substrate comprises a material selectedfrom the group consisting of steel, aluminum, magnesium, alloys, andcombinations thereof.
 8. The coated article of claim 1 wherein thefoundation coat is covalently bonded to the metallic substrate, andwherein the covalent bonding between the foundation coat and themetallic substrate ranges from greater than or equal to 60 kJ/mol toless than or equal to about 800 kJ/mol.
 9. A method for forming thecoated article of claim 1, the method comprising: incorporating theplurality of capsules in a sol matrix to form a foundation coatprecursor, each capsule including a shell capable of covalently bondingto the sol matrix and a healing agent surround by the shell, and whereinthe sol matrix comprises titania or silica nanoparticles suspended in aliquid comprising water, ethanol, or butyl acetate; and wherein thecross-linked titania or silica nanoparticles are compatible with the solmatrix; applying the foundation coat precursor on the metallicsubstrate; and heating the foundation coat precursor and metallicsubstrate in order to cure the foundation coat precursor and form afoundation coat, wherein the foundation coat is covalently bonded to themetallic substrate.
 10. The coating method of claim 9, wherein applyingthe foundation coat precursor includes dipping the metallic substrate ina tank containing the foundation coat precursor.
 11. The coating methodof claim 9, wherein heating the foundation coat precursor and metallicsubstrate includes positioning the metallic substrate in an oven afterapplying the foundation coat precursor on the metallic substrate andheating the coated metallic substrate at a temperature between 200degrees Fahrenheit and about 320 degrees Fahrenheit for a time betweenabout 15 minutes and about 50 minutes.
 12. A precursor of a coating foran article, the precursor comprising: a sol matrix comprising titania orsilica nanoparticles suspended in a liquid comprising water, ethanol, orbutyl acetate; and a plurality of capsules present in the sol matrix,each capsule including a shell that is capable of covalently bonding tothe sol matrix and a healing agent surrounded by the shell, wherein thehealing agent is an alcohol based sol gel material comprising titania orsilica nanoparticles and is compatible with the sol matrix.
 13. Theprecursor of claim 12, wherein the plurality of capsules comprises aplurality of first capsules and a plurality of second capsules, whereinthe first capsules include a resin as a first healing agent and thesecond capsules include a curing agent of the resin as a second healingagent.
 14. The precursor of claim 13, wherein the resin of the firstcapsule is a vinyl terminated polydimethylsiloxane (PDMS) resin and thecuring agent of the second capsules is a polyisocyanate resin.
 15. Theprecursor of claim 12, wherein the sol matrix has a nanoparticleconcentration of 25 wt. % and the plurality of capsules has ananoparticle concentration of 40 wt. %.
 16. The precursor of claim 12,wherein the sol matrix has an amount of the capsules ranging from about1 wt. % to about 40 wt. % of a total wt. % of the sol matrix.
 17. Theprecursor of claim 12, wherein the shell is selected from the groupconsisting of titania, silicon dioxide, quartz crystal, and silicaglass.